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On the mechanism of particle formation above the CMC in emulsion polymerization

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Abstract

The mechanism of particle nucleation has great influence on the kinetics and the particle size distribution of polymer latexes produced in emulsion polymerization. These are key aspects for the application of these products and for the development of emerging processes, such as living/controlled free-radical polymerizations. One very popular theory publish in the 80s establishes that the new-born (primary) particles undergo limited coagulation even when the concentration of surfactant is above its critical micellar concentration. In this communication, the experiment that was the base for the formulation of such theory is reexamined and discussed to determine whether it can be considered as “typical condition”, such that the general character of their conclusions can be justified. In this context, the positive skewness of the PSD observed in that time and taken as an evidence of the coagulative nucleation is discussed as well.

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References

  1. González-Blanco R, Saldívar-Guerra E, Herrera-Ordóñez J, Cano-Valdez A (2013) TEMPO Mediated Radical Emulsion Polymerization of Styrene by Stepwise and Semibatch Processes. Macromol Symp 325–326:89–95

    Article  Google Scholar 

  2. Hassan M, Reddy KR, Haque E, Minett AI, Gomes VG (2013) High-yield aqueous phase exfoliation of graphene for facile nanocomposite synthesis via emulsion polymerization. J Colloid Interface Sci 410:43–51

    Article  CAS  Google Scholar 

  3. Khan MU, Reddy KR, Snguanwongchai T, Haque E, Gomes VG (2016) Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization. Colloid Polym Sci 294:1599–1610

    Article  CAS  Google Scholar 

  4. Sheibat-Othman N, Vale HM, Pohn JM, McKenna TFL (2017) Is Modeling the PSD in Emulsion Polymerization a Finished Problem? An Overview. Macromol React Eng. doi:10.1002/mren.201600059

    Google Scholar 

  5. Priest WJ (1952) Partice Growth in the Aqueous Polymerization of Vinyl Acetate. J Phys Chem 56:1077–1082

    Article  CAS  Google Scholar 

  6. Fitch RM, Tsai CH (1971) Particle formation in polymer colloids, III: Prediction of the number of particles by a homogeneous nucleation theory. In: Fitch RM (ed) Polymer colloids. Plenum, New York, pp 73–102

    Chapter  Google Scholar 

  7. Fitch RM, Tsai CH (1971) Particle formation in polymer colloids, IV: the role of soluble oligomeric radicals. In: Fitch RM (ed) Polymer colloids. Plenum, New York, pp 103–116

    Chapter  Google Scholar 

  8. Hansen FK, Ugelstad J (1978) Particle nucleation in emulsion polymerization. I. A theory for homogeneous nucleation.  J Polym Sci Polym Chem Ed 16:1953–1979

    Article  CAS  Google Scholar 

  9. Harkins WD (1947) A General Theory of the Mechanism of Emulsion Polymerization. J Am Chem Soc 69:1428–1444

    Article  CAS  Google Scholar 

  10. Smith WV, Ewart RH (1948) Kinetics of Emulsion Polymerization. J Chem Phys 16:592–599

    Article  CAS  Google Scholar 

  11. Hansen FK, Ugelstad J (1979) Particle nucleation in emulsion polymerization. III. Nucleation in systems with anionic emulsifier investigated by seeded and unseeded polymerization. J Polym Sci Polym Chem Ed 17:3047–3067

    Article  CAS  Google Scholar 

  12. Harada M, Nomura M, Kojima H, Eguchi W, Nagata S (1972) Rate of emulsion polymerization of styrene. J Appl Polym Sci 16:811–833

    Article  CAS  Google Scholar 

  13. Nomura M, Harada M, Eguchi W, Nagata S (1976) Kinetics and Mechanism of the Emulsion Polymerization of Vinyl Acetate. ACS Symp Ser 24:102–121

    Article  CAS  Google Scholar 

  14. Nomura M, Satpathy US, Kouno Y, Fujita K (1988) Investigation on the locus of particle formation in emulsion polymerization containing partially water-soluble monomers. J Polym Sci Polym Part C 26:385–390

    CAS  Google Scholar 

  15. Nomura M, Fujita K (1994) Kinetics and Mechanisms of Unseeded Emulsion Polymerization of Methyl Methacrylate. Polym React Eng 2(4):317–345

    Article  CAS  Google Scholar 

  16. Herrera-Ordóñez J, Olayo R (2001) Methyl methacrylate emulsion polymerization at low monomer concentration: Kinetic modeling of nucleation, particle size distribution, and rate of polymerization. J Polym Sci Part A Polym Chem 39:2547–2556

    Article  Google Scholar 

  17. Odian G (2004) Principles of polymerization. Wiley, New Jersey, pp 350–371

    Book  Google Scholar 

  18. Herrera-Ordonez J, Olayo R, Carro S (2004) The Kinetics of Emulsion Polymerization: Some Controversial Aspects. J Macromol Sci Part C Polym Rev C44:207–229

    Article  CAS  Google Scholar 

  19. Lichti G, Gilbert RG, Napper DH (1983) The mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate. J Polym Sci Polym Chem Ed 21:269–291

    Article  CAS  Google Scholar 

  20. Morrison BR, Maxwell IA, Gilbert RG, Napper DH (1992) Testing Nucleation Models for Emulsion-Polymerization Systems. ACS Symp Ser 492:28–44

    Article  CAS  Google Scholar 

  21. Nomura M, Harada M, Eguchi W, Nagata S (1972) Effect of stirring on the emulsion polymerization of styrene. J Appl Polym Sci 16:835–847

    Article  CAS  Google Scholar 

  22. Gilbert RG (1995) Emulsion polymerization: a mechanistic approach. Academic, London, p 231

    Google Scholar 

  23. Shastry V, Garcia-Rubio LH (2006) Identification of nucleation loci in emulsion polymerization processes. I. New information from spectroscopy studies. J Appl Polym Sci 100:2847–2857

    Article  CAS  Google Scholar 

  24. Tauer K, Hernandez H, Kozempel S, Lazareva O, Nazaran P (2008) Towards a consistent mechanism of emulsion polymerization—new experimental details. Colloid Polym Sci 286:499–515

    Article  CAS  Google Scholar 

  25. Herrera-Ordóñez J, Olayo R (2000) On the kinetics of styrene emulsion polymerization above CMC. II. Comparison with experimental results. J Polym Sci Part A Polym Chem 38:2219–2231

    Article  Google Scholar 

  26. Carro S, Herrera-Ordonez J (2006) Styrene Emulsion Polymerization above the CMC: New Evidence on Particle Nucleation by means of AFFFF. J Macromol Rapid Commun 27:274–278

    Article  CAS  Google Scholar 

  27. Carro S, Herrera-Ordonez J, Castillo-Tejas J (2010)  On the evolution of the rate of polymerization, number and size distribution of particles in styrene emulsion polymerization above CMC. J Polym Sci Part A Polym Chem 48:3152–3160

    Article  CAS  Google Scholar 

  28. Coen EM, Gilbert RG, Morrison BR, Leube H, Peach S (1998) Modelling particle size distributions and secondary particle formation in emulsion polymerisation. Polymer 39:7099–7112

    Article  CAS  Google Scholar 

  29. Varela de la Rosa L, Sudol ED, El-Aasser MS, Klein A (1996) Details of the emulsion polymerization of styrene using a reaction calorimeter. J Polym Sci Part A Polym Chem 34:461–473

    Article  Google Scholar 

  30. Araújo PEH, de la Cal JC, Asua JM, Pinto JC (2001) Modeling particle size distribution (PSD) in emulsion copolymerization reactions in a continuous loop reactor. Macromol Theory Simul 10:769–779

    Article  Google Scholar 

  31. Tauer K (1998) Comment on the Development of Particle Surface Charge Density during Surfactant-Free Emulsion Polymerization with Ionic Initiators. Macromolecules 31:9390–9391

    Article  CAS  Google Scholar 

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Acknowledgements

JHO thanks the financial support of Consejo de Ciencia y Tecnología del Estado de Querétaro (CONCyTEQ, México) through the Nuevos Talentos Program 2016. SC and JCT thank financial support of CONACyT under Grant 84472. The authors thank Miss M. Isabel Linares-Núñez and Miss Sonia Hernández-Huerta for their help in carrying out the polymerizations.

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Authors and Affiliations

  1. Facultad de Ciencias Básicas, Ingeniería y Tecnología, Universidad Autónoma de Tlaxcala, Calzada Apizaquito s/n, CP 90300, Apizaco, Tlaxcala, Mexico

    Shirley Carro & Jorge Castillo-Tejas

  2. Centro de Física Aplicada y Tecnología Avanzada (CFATA), UNAM Campus Juriquilla, Blvd. Juriquilla 3001, CP 76230, Juriquilla, Querétaro, Mexico

    Jorge Herrera-Ordonez

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  1. Shirley Carro
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  2. Jorge Herrera-Ordonez
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  3. Jorge Castillo-Tejas
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Correspondence to Jorge Herrera-Ordonez.

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Carro, S., Herrera-Ordonez, J. & Castillo-Tejas, J. On the mechanism of particle formation above the CMC in emulsion polymerization. Polym. Bull. 75, 1027–1035 (2018). https://doi.org/10.1007/s00289-017-2075-2

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  • DOI: https://doi.org/10.1007/s00289-017-2075-2

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